Xinxing Peng, Philipp M. Pelz, Qiubo Zhang, Peican Chen, Lingyun Cao, Yaqian Zhang, Hong-Gang Liao, Haimei Zheng, Cheng Wang, Shi-Gang Sun, Mary C. Scott. Our results show a multistep formation process, where precursor clusters first form in solution, then they are complexed with ligands to form non-crystalline solids, followed by the arrangement of the cluster-ligand complex into crystalline sheets, with additional possible growth by the addition of clusters to surface edges. Moreover, high-resolution imaging allows us to identify missing clusters, dislocations, loop and flat surface terminations and ligand connectors in the MOLs. Our observations provide insights into controllable MOL crystal morphology, defect engineering, and surface modification, thus assisting novel MOL design and synthesis.

凌誉, 曹凌云, 林昶旭, 周达, 汪骋。 自动化技术已在现代制造业中广泛应用, 但化学合成研发工作的自动化程度较低, 仍大量依赖于化学工 作者的手工操作. 这主要是因为经典的自动化技术的智能化程度不高, 难以应用于具有流程多样性和结果不确定 性的化学研发. 然而, 以物联网、协作机器人、人工智能为代表的新一代自动化技术已经能够实现更灵活的部署 和更智能的运作, 具备了与化学合成与材料研发深度融合的条件. 以“无人实验室”为目标的自动化和智能化的化 学合成系统正在蓬勃发展. 本文对该领域近年来的发展进行了梳理, 并对未来的发展进行了展望.

Yuming Su, Yiheng Dai, Yifan Zeng, Caiyun Wei, Yangtao Chen, Fuchun Ge, Peikun Zheng, Da Zhou*, Pavlo O. Dral*, Cheng Wang. Here a systematic study is performed by collecting an experimental TPA database with ≈900 molecules, analyzing with interpretable machine learning (ML) the key molecular features explaining TPA magnitudes, and building a fast ML model for predictions.

Jiawei Chen, Han Li, Haoshang Wang, Yuhang Song, Qiming Hong, Kuan Chang, Huihui Hu, Shuhong Zhang, Lingyun Cao, Cheng Wang. Metal–organic layers (MOLs) are versatile platforms for creating single-site heterogeneous catalysts. Incorporating molecular functionalities into MOLs is crucial for catalysis. In this study, we synthesized phosphine-containing MOLs constructed from Hf6-oxo secondary building units (SBUs) and phosphine ligands. The mono(phosphine)-Ir complexes generated by the metalation of TPP-MOL were highly active as heterogeneous catalysts for the C(sp2)–H borylation of a range of arenes. This research expands the diversity of MOL-based catalysts.

Xuefeng He, Lina Zhang, Jiawei Chen, Huichong Liu, Yu-Ming Su, Han Li, Yonghua Cao, Pavlo O. Dral*, Cheng Wang. Conversion of methane to liquid oxygenates is challenging but of great value. Here, we report the oxidation of methane (CH4) to methanol (CH3OH) assisted by nitrogen dioxide (NO2) as a photo-mediator and using molecular oxygen (O2) as the terminal oxidant.

Yusheng Zhang, Yuming Su, Xiaolin Fan, Boxuan Zhao, Xin Hua, Bingling Dai, Cheng Wang* Three‐dimensional (3D) patterning of fluorescent structures in metal‐organic frameworks (MOFs) is useful for fabricating MOF‐based devices for sensing and data storage. This work creates 3D multicolor patterns in an MOF crystal by sequentially printing different substructures with different dye molecules incorporated. Printed multicolor 3D arrays inside MOF crystal are used for 3D optical data storage. Each color dot can represent four‐digit information 0, 1, 2, 3 as compared to the 0,1 by a bit, using three colors plus the blank to convey the information. Through the combination of different initiator molecules of different emission colors, the data storage density is expected to increase further.

Huihui Hu, Yuming Su, Xiaoqi Cui, Boxuan Zhao, Jiawei Chen, Suyang Chen, Manting Chen, Haohua Huo, Cheng Wang. Controlling regioselectivity in activating C–H bonds in linear alkanes is challenging, as their multiple secondary C–H bonds have quite similar dissociation energies, with no functional groups to differentiate between the bonds. Here, we coupled a ligand-to-metal charge transfer (LMCT)-based radical generation center and an amide functional group on a tailor-designed metal-organic layer (MOL) material. We achieved efficient photochlorination of linear alkanes with 2-position selectivity.

Xuefeng He, Zihan Wang, Xinru He, Huichong Liu, Jiawei Chen, Han Li, Prof. Cheng Wang. A metal-free natural dye has been developed to selectively convert methane to methyl trifluoroacetate (CH3TFA) using visible light, probably due to the formation of a chloride-bridged dimer undergoing fast intra-complex charge transfer.

Xinru He, Yuming Su, Jieyu Zhu, Nan Fang, YangTao Chen, Huichong Liu, Da Zhou and Cheng Wang. In this work, we analyzed the literature data on the catalytic performance of organics-modified Cu and bare Cu for comparison. We calculated the change in the faradaic efficiency of C2+ products after organic modification. We analyzed these changes using machine learning, which showed an unexpected correlation between the electronic structure of the modifiers and the faradaic efficiency.

Xinru He, Ying Guo, Jingzheng Zhang, Shuangli Yang, Jiawei Chen, Shurong Li, Shunji Xie, Ye Wang and Cheng Wang. Metal NP @ metal–organic frameworks (MOFs) are widely used in electrocatalysis. However, many of the MOFs are poorly conductive. Here, we loaded bismuth (Bi) into a Zr-based MOF of the UiO structure that is active for CO2 reduction to formate and found that a moderate conductivity of the nanosized MOFs is sufficient to support a reasonably high catalytic current density. This finding allows simpler catalyst design and quantitative rationalization of MOF electrocatalysis.

Xin-Jing Zhao Xin-Jing Zhao, Yang-Yang Ju, Yu-Ming Su, Chun Tang, Qi Zeng, LiuBin Feng, Cheng Wang*, Klaus Müllen, and Yuan-Zhi Tan The conventional approach toward molecules with large two-photon absorption (TPA) involves donor-acceptor conjugation.

Zhiye Wang, Bingling Dai, Yuming Su, Huihui Hu, Xinru He, Jiawei Chen, and Cheng Wang This study focuses on a MOF of the UiO-68 structure, which is built from a fluorescent dibenzoate-anthracene ligand doped with a dibenzoate-benzene ligand.

Jing Wang, Han Li, Jiawei Chen and Cheng Wang. This design not only leads to a stable catalytic operation but also constitutes a clean HCHO-to-DHA conversion system. This oligomerization of formaldehyde to DHA completes a critical step in converting CO2 to sugar, including CO2 hydrogenation to methanol (CH3OH), CH3OH oxidation to HCHO, HCHO oligomerization to DHA, and DHA condensation to higher carbohydrates.

Ting Tang, Yiheng Dai, Jiaxing Liu, Jiawei Chen, Bingling Dai, Boxuan Zhao, and Cheng Wang* In this study, we investigated a series of Zr-based MOFs with different secondary building units (SBUs) and pore sizes as the Fe support and found that MIL140-BPDC-Fe exhibited the highest photocatalytic oxidation of cyclohexane under visible light irradiation (TONcyclohexane = 6914, conversion = 26.2%, apparent quantum yield (AQY) = 5%).

Ming-Hao Du, Yiheng Dai, Lin-Peng Jiang, Yu-Ming Su, Ming-Qiang Qi, Cheng Wang*, La-Sheng Long, Lan-Sun Zheng, and Xiang-Jian Kong* J. Am. Chem. Soc. 2023, 145, 42, 23188–23195 Inorganic molecular cages are emerging multifunctional molecular-based platforms with the unique merits of rigid skeletons and inherited properties from constituent metal ions. However, the sensitive coordination bonds and vast synthetic space have limited their systematic exploration.

Yuming Su, Yiheng Dai, Yifan Zeng, Caiyun Wei, Yangtao Chen, Fuchun Ge, Peikun Zheng, Da Zhou, Pavlo O. Dral, Cheng Wang First published: 19 January 2023 https://doi.org/10.1002/advs.202204902 Molecules with strong two-photon absorption (TPA) are important in many advanced applications such as upconverted laser and photodynamic therapy, but their design is hampered by the high cost of experimental screening and accurate quantum chemical (QC) calculations. Here a systematic study is performed by collecting an experimental TPA database with ≈900 molecules, analyzing with interpretable machine learning (ML) the key molecular features explaining TPA magnitudes, and building a fast ML model for predictions. The ML model has prediction errors of similar magnitude compared to experimental and affordable QC methods errors and has the potential for high-throughput screening as additionally validated with the new experimental measurements.

Cankun Zhang, Yuzhe Zhang, Zhiye Wang, Yuming Su, Zhixiang Wei, Jianhui Hou, Shan He, Kaifeng Wu, Chang He, Jianqi Zhang & Cheng Wang Science China Chemistry volume 64, pages1569–1576 (2021) A bulk heterojunction in organic solar cells is where charge separation and recombination occur. Molecular orientation at the interface is one of the key factors that dictate solar cell efficiency. Although X–ray scattering-based methods can determine donor/acceptor domain orientations between an anisotropic phase and an isotropic fullerene-based phase, the rise of non-fullerene solar cells presents a new challenge in delineating local molecular directions at the interface between two anisotropic donor/acceptor domains.

Zhiye Wang, Yusheng Zhang, Yuming Su, Cankun Zhang & Cheng Wang Science China Chemistry volume 65, pages2283–2289 (2022)

Mingcan Xie, Yan Shen, Wenchao Ma, Diye Wei, Biao Zhang, Zihan Wang, Yihan Wang, Prof. Qinghong Zhang, Prof. Shunji Xie, Prof. Cheng Wang, Prof. Ye Wang First published: 26 October 2022 https://doi.org/10.1002/anie.202213423 By using an automatic fast screening platform, a magnesium-modified copper catalyst has been discovered to be very efficient for electrocatalytic CO2 reduction reaction (CO2RR) to C2+ compounds. This catalyst, achieving 80 % C2+ Faradaic efficiency at a current density of 1.0 A cm−2, stands out from 109 Cu-based bimetallic catalysts evaluated within only 55 hours. The modification by magnesium enhances the activation of CO2 and stabilizes Cu+ to facilitate the CO adsorption and C−C coupling.

Jiawei Chen,‡a Zhi Ye,‡a Peican Chen,‡b Huihui Hu,a Shuhong Zhang,a Han Xu,a Lingyun Cao*ac and Cheng Wang https://doi.org/10.1039/D2DT01239AFirst published 29 Jun 2022 Metal–organic layers (MOLs), a category of two-dimensional materials, have attracted wide interest due to their molecular tunability and the ease of surface modification. Herein, we reported the synthesis and structural determination of a free-standing MOL, {[Hf6O8H4(HCOO)2(H2O·OH)4]3[Hf12O16H8(HCOO)6.8(H2O·OH)11.2](TPO)8}n, constructed from Hf6-oxo and Hf12-oxo clusters as secondary building units (SBUs) and the tris(4-carboxylphenyl)phosphine oxide (TPO) ligand. We establish a structure model of this new MOL based on the combined information from different characterization methods.

Jing Wang,a Huichong Liu,a Jiawei Chen,a Lingyun Cao*b and Cheng Wang DOI https://doi.org/10.1039/D2CC01114J First published 25 Apr 2022 Alcohols are attractive portable chemical carriers of hydrogen thanks to their reversible dehydrogenation, but the hydrogen release reaction is thermodynamically unfavorable. Coupling the alcohol dehydrogenation to acetal formation can shift the reaction thermodynamics for hydrogen production. Here, we stabilized Ir3+ and Sc3+ in a metal–organic framework (MOF) for tandem catalysis. The Ir3+ center bearing an α-hydroxybipyridine ligand catalyzes alcohol dehydrogenation, and the Sc3+ Lewis acid site catalyzes acetal formation that allows further dehydrogenation to form esters. The bifunctional UiO-bpyOH–IrCp–Sc catalyst effectively converts ethylene glycol to ester and H2 without producing CO.

Ying Huang,a Yusheng Zhang,a Yuming Su,a Zhenghao Zhai,a Jiawei Chena and Cheng Wang Chem. Commun., 2021,57, 4516-4519 Two-photon induced polymerization for three-dimensional (3D) printing has attracted increasing attention. Here, we report the two-photon induced polymerization of triethylene glycol divinyl ether (TEGDVE) in a porous polymer film using 4,4′,4′′-nitrilotribenzoic acid (NTB) as the photosensitizer and diphenyliodonium hexafluorophosphate (HIP) as the initiator, enabling the printing of multi-layer structures in the porous support.

Lingzhen Zeng, Yonghua Cao, Zhe Li, Yiheng Dai, Yongke Wang, Bing An, Jingzheng Zhang, Han Li, Yang Zhou, Wenbin Lin, and Cheng Wang* September 7, 2021 https://doi.org/10.1021/acscatal.1c01939 Hydrogenation of carbon dioxide (CO2) to ethylene (C2H4) can be achieved in two routes via tandem reactions: (1) CO2 hydrogenation to methanol (CH3OH) followed by methanol-to-olefin conversion and (2) reverse water-gas shift reaction followed by Fischer–Tropsch synthesis. Here we present another tandem route for CO2-to-C2H4 conversion via (3) CO2 hydrogenation to ethanol (C2H5OH) followed by C2H5OH dehydration. Multiple cuprous (CuI) centers were loaded onto the Ti8(μ2-O)8(μ2-OH)4 secondary building units of a Ti-based metal–organic framework (MOF), MIL-125-NH2, via deprotonation and ion exchange of the μ2-OH groups.

Jingzheng Zhang, Bing An, Yonghua Cao, Zhe Li, Jiawei Chen, Xuefeng He, and Cheng Wang* Publication Date:November 21, 2021 https://doi.org/10.1021/acsaem.1c02175 ZnO supported on ZrO2 is active in hydrogenating CO2 to methanol. The local structure at the ZnO/ZrO2 interface must play an important role in catalysis. Here, we support ZnO on Zr-based metal–organic framework (MOF) nanoplates to construct an active catalyst for CO2 hydrogenation to methanol. Compared to ZrO2, the Zr-based MOF has a better-defined local structure on the surface. The Zr-based MOF contains Zr12(μ3-O)8(μ3-OH)8(μ2-OH)6 clusters connected by linear biphenyldicarboxylate (bpdc) linkers. No aggregation of the ZnO nanoparticles was observed after the catalysis of 100 h at 250 °C.